CN1037331A

CN1037331A - The method for preparing lower dialkyl disulphides

Info

Publication number: CN1037331A
Application number: CN89102270A
Authority: CN
Inventors: 亨利·冈戈拉; 维斯·达奇
Original assignee: Elf Aguiyuan National Petroleum Manufacturing Co
Current assignee: Elf Aguiyuan National Petroleum Manufacturing Co
Priority date: 1988-04-14
Filing date: 1989-04-14
Publication date: 1989-11-22
Anticipated expiration: 2004-04-14
Also published as: CN1026233C; EP0337839A1; KR910009129B1; US5001269A; KR890016004A; JPH026466A; FR2630105B1; JPH0639459B2; CA1322765C; DE68900010D1; EP0337839B1; FR2630105A1; ES2018093B3

Abstract

The invention relates to the method for preparing R-SS-R type dialkyl disulphides, wherein the R representative has the alkyl of 1-3 carbon atom, this method is to be the composition of alkyl sulfhydryl R '-SH and olefin oxide and alkali with the corresponding alkylide RSH. of sulphur oxidation catalyst system therefor in the presence of catalyzer, and R ' is the alkyl with 6 to 18 carbon atoms.Use this catalyzer can obtain the lower dialkyl disulphides (do not have amine and be not with color) of superperformance.

Description

The method for preparing lower dialkyl disulphides

The present invention relates to the organic disulfide field, more particularly, its objective is preparation lower dialkyl disulphides R-SS-R, wherein R represents an alkyl with 1-3 carbon atom.

Important preparation approach about this disulphide comprises according to following reaction path usefulness sulphur oxidation of alkyl mercaptan in the presence of catalyzer: In this method, may there be different second order reactions, particularly: Excessive alkyl sulfhydryl and remove the generation that hydrogen sulfide has promoted dialkyl disulphides.

The catalyzer of Shi Yonging is an aliphatic amine the most frequently, particularly triethylamine (United States Patent (USP) 2,237,625, French Patent 1,358,398, United States Patent (USP) 3,299,146 and French Patent 2,130,985).The latter also has shortcoming, is promptly partly kept in final disulphide, becomes impurity and makes product have undesirable color.In addition, for the pre-treatment of hydrocracking catalyst, the certain user of disulphide tends to use the product that does not conform to nitrogen.

Have been found that, olefin oxide and alkali and senior alkyl thioalcohol R '-SH are made up with being catalyzer, can not influence the output of factory and obtain having, not with the amine impurity and the unusual dialkyl disulphides of light colour than good quality.In addition, in the continuous production factory of dialkyl disulphides,, also recyclable and be circulated to the advantage of synthesis reactor according to the trialkylamine of combination catalyst of the present invention compared with prior art.

The objective of the invention is in the presence of catalyzer, corresponding alkyl sulfhydryl R-SH and sulphur to be carried out the method that the oxidizing reaction fork-like farm tool used in ancient China prepares lower dialkyl disulphides R-SS-R (wherein the R representative has the alkyl of 1-3 carbon atom), it is characterized in that catalyst system therefor is the composition of senior alkyl thioalcohol R '-SH and olefin oxide and alkali,, this composition can be represented by the formula:

R '-SH.x (C _nH _2nO) .yMOH wherein R ' be a straight or branched alkyl with 6-18 carbon atom, n is the number of 2-4, x is the number of 1-20, y is the number of 0.01-1, M is a basic metal, preferably sodium or potassium.

Composition use preferably is that wherein R ' is C8-C16 tertiary alkyl (for example uncle's nonyl or uncle's dodecyl).Every mole of mercaptan R '-SH relatively, the mole number X of olefin oxide is 4-12, the mole number Y of alkali is 0.1-0.5.Preferably both economical ethylene oxide is used as olefin oxide, and still, available if desired propylene oxide or oxybutylene replace or mix with it.

According to the present invention, a kind of method of Preparation of Catalyst comprises that (α=1-1.5) alkali MOH tentatively mixes, and is preferably in heating this mixture of homogenizing down with α Y mole with 1 mole of mercaptan R ' SH; This process is preferably under 50 ℃-100 ℃ carried out several hours, particularly carried out 4-6 hours under 75 ℃-85 ℃.Then, the liquid injection olefin oxide CNH2NO to this method gained can introduce required ratio X like this; This injection method is preferably under 0.2-4 bar pressure and 80-120 ℃ according to the character of used mercaptan R ' SH and carries out, and the introducing of olefin oxide generally needs 1-10 hour.After finishing these processes, suggestion outgases reaction mixture with rare gas element such as nitrogen and removes superfluous olefin oxide, filter gained liquid then before being used as the catalyzer of the inventive method.

The amount of catalyst system therefor is with respect to the 0.2-5% of the weight of used sulphur in the oxidizing reaction of preparation disulphide RSSR, is preferably 1.5-4%.

The same with known method, the mol ratio of mercaptan RSH and sulphur equals 2 at least, is preferably 3-

Oxidizing reaction is carried out under 25-125 ℃, and working pressure is 1-5, is preferably the 3-4 crust.Preferred temperature depends on used mercaptan RSH; For the methyl mercaptan temperature is 50-60 ℃, is 60-70 ℃ for the ethanethio temperature, is 70-80 ℃ for propyl group mercaptan temperature.

Though combination catalyst of the present invention can be used for preparing in the discontinuous method of dialkyl disulphides R-SS-R, more properly say in the continuous processing production dialkyl disulphides of estimating to use it in the factory.

Accompanying drawing is the flow process of this plant produced of explanation, and it is particularly including reactor 1, degassing tower 2 and distilling column 3.

Reactant is: liquid sulfur, mercaptan RSH (liquid state or gaseous state) and catalyst (or from the next bottoms of tower 3 bottom cycle), they are respectively by pipe 4,5 and 6 add in the reactor 1 continuously, this reactor is to have temperature commonly used, the conditioning equipment of pressure and content, and material and heat transmission can be guaranteed in outside circulation road 7. The holdup time of reactant in this reactor is 20-180 minute, preferably 30-90 minute, and even more preferably about 1 hour. Off-gas is discharged to the exterior tubing by managing 8 tops from reactor, and crude reaction liquid is discharged from the bottom of reaction, enters degassing tower 2 by managing 9.

Packed tower with hot water circuit and the entrance of inert gas such as methane or nitrogen makes most of common hydrogen sulfide that produces separate with most of excessive alkyl hydrosulfide RSH. Then the latter sends into heat exchange by managing 10--and condenser, then herein condensation directly or by hold-up tank is circulated to reactor 1. In the bottom of tower 2, crude product reclaims, and it comprises required dialkyl disulphides RSSR, corresponding polysulfide (mainly being the dialkyl group trisulfide), catalyst and a small amount of alkyl hydrosulfide.

Crude product enters tower 3 by managing 11, and distilled reduces pressure in tower. Required dialkyl disulphides in recovered overhead, mainly contains dialkyl disulphides by pipe 12 this moment in the bottom. The mixture of dialkyl group trisulfide and catalyst, they are recycled in the reactor 1 by managing 13 and 6.

Following example explanation the present invention, but do not limit it.A) Preparation of catalysts

In 150 liters stainless steel reactor, add 68Kg (336.6 moles) uncle's lauryl mercaptan C12H25SH and 6.3Kg (157.5 moles) anhydrous Na oH, heat 5 hours down to guarantee that mixture carries out good dispersion and homogenizing at 80 ℃ then.Then, ethylene oxide with 7Kg in the continuous output speed injecting reactor of h 8 hours; Relative pressure in reactor becomes 4 crust when adding by initial 0.2 crust.Thereafter, reaction mixture heated 2 hours down at 100 ℃-110 ℃, reduced pressure then and outgased to remove all dissolved excessive oxidation ethene with one nitrogen.Then the gained liquids is filtered to remove the solid particulate greater than 5 microns.

Combination catalyst with this method gained has following mole composition:

C ₁₂H ₂₅SH，6(CH ₂CH ₂O)，0.35NaOH

Wherein by weight:

C ₁₂H ₂₅SH...........42％

CH ₂CH ₂O?...........55％

NaOH??????...........?3％

The cloud point of this catalyzer is about 62 ℃.

B) dimethyl disulphide is synthetic continuously

This reaction can be carried out in the above-mentioned type factory.Import continuously in the reactor 1 10Kg the h liquid sulfur, 55Kg liquid methyl mercaptan of h and 0.35Kg/h method A) the described catalyzer that obtains.When reaction reaches balance (after about 12 hours), replace speed enter catalyst with the product that comes from distillation tower 3 bottoms of 7Kg/h circulation input with 0.35Kg/h, this product contains the 0.35Kg catalyzer, 3.64Kg DMDS and 3.01Kg polysulfide mainly are dimethyl trisulfide (DMTS).

This is reflected at 55-58 ℃ is to carry out under 3.5 crust with working pressure, and the average retention time of reactant in reactor is about 1 hour.Come the liquid crude reaction thing of autoreactor to be transfused to tower 2, outgas down at 65-70 ℃ at this industrial gas (methane) with one 6Nm/h.

The 37.26Kg/h liquid object is reclaimed in bottom by tower 2, and this liquid object contains 85.70%DMDS by weight, 12.23%DMTS, 1.13% methyl mercaptan and 0.94% catalyzer.This liquid object is transfused to distillation tower 3, in this fractionation under following condition:

The about 37Kg/h of input speed

The about 28.1Kg/h of distillation output

The about 8.5Kg/h of bottom output

Dividing potential drop 13.33KPa at the top

56 ℃ of head temperature

Bottom temp 90-100 ℃

At the top of tower, can obtain purity and be 99% 28.1Kg/h DMDS, be 95% with respect to used sulphur productive rate.The DMDS that makes with this method has very weak color; It does not contain amine impurity, sodium hydroxide and oxygen, and its CS2 residuals content is less than 500PPM.

Reclaim the 8.3Kg/h mixture from the bottom of tower, this mixture contains weight and is about 43.85% DMDS, 29.05% DMTS, 4.2% catalyzer and 22.9% senior polysulfide.After the filtration, obtain the 7Kg/h product, wherein contain 5% catalyzer of having an appointment, 52%DMDS and 34.4% DMTS.In case reaction reaches balance, this product is as the substituent input of raw catalyst.

Claims

1. the method for preparing R-SS-R type lower dialkyl disulphides, wherein the R representative has the alkyl of 1-3 carbon atom, this method is with the corresponding alkyl sulfhydryl RSH of sulphur oxidation in the presence of catalyzer, it is characterized in that catalyst system therefor is the composition of senior alkyl thioalcohol R '-SH and olefin oxide CnH2nO and alkali MOH, this composition can be represented by the formula:

R '-SH.x (C _nH _2nO) .yMOH wherein R ' be a straight or branched alkyl with 6-18 carbon atom, n is the number of 2-4, x is the number of 1-20, y is the number of 0.01-1, M is an alkali metal atom.

2. according to the method for claim 1, it is characterized in that wherein R ' is the C8-C16 tertiary alkyl, preferably uncle's nonyl or uncle's dodecyl.

3. according to the method for claim 1 or 2, it is characterized in that wherein n is 2, x is that 4-12 and y are 0.1-0.5.

4. according to the method for one of claim 1 to 3, it is characterized in that catalyst consumption wherein with respect to adding sulphur weight be 0.2-5%, the mol ratio of mercaptan RSH and sulphur is at least 2, is preferably 3-5.

5. according to the method for one of claim 1 to 4, it is characterized in that wherein reacting is 125 ℃ of 25-, preferably under 50-80 ℃, and is 1-5 in working pressure, is preferably under the 3-4 crust and carries out.

6. according to the method for one of claim 1 to 5, it is characterized in that wherein reacting is successive, and the residence time is 20-180 minute in reactor, preferably 30-90 minute.

7. according to the method for one of claim 1 to 6, it is characterized in that wherein alkyl sulfhydryl RSH is a methyl mercaptan.